Detergent and method of making the same



April 14, 1953 H. A. MOLTENI ET AL DETEEGENT AMD METHOD oE MAKING THE sAME Filed March 9. 1950 Patented Apr. 14,1953

oo oFMAniNo v.DETERGEN'I AND TH E SAME` Henry A. Molteni, Dover, and Nathaniel H. Masarky, Teaneck, N. J., and George .Barslm .New York, N. L, assignors. to E...E. .Drew & Co., Inc., New YiZorlt, N. Y.,4 a .corporation of Dela- Walle .8 Claims.

Y The present inventionis directed to .detergents and more particularly to synthetic .detergents .and compositions containing the same, and .methods of making such detergents.

- The present `invention .has among its .objects theprovisions of a method of making condensa-.- tion products usable for detergent purposes which is simple and highly effective, and is adapted to large scale operation with controllable and reproe ducible results.

.It 'is also among the objects of the present Vinventlon to provide a `condensation product which is stable, light in color, 'highly resistant to rancidity and having excellent detergent properties.

Itis further among the objects of the present invention to provide a shampoo composition including said condensation product which is smooth, stable over a long period of time under 'adverse conditions and highly elective in its `detergent properties.

Itis still further among `the objects vof the prese ent invention to provide a detergent inthe .form of a cake, which is coherent and does not .disintegrate on handlingJ which is suflicientlysoluble -toenable its use in ordinary Washing operations and which may be readily produced on .a large scale.

In practicing the present invention there is *proa vided ra Water-soluble salt of hydroxyethylsul phuric acid. This is mixed with a fatty acid or a mixture of fatty acids .and preferably the higher saturated fatty acids. For example, one may use the .fatty aci-ds obtained by hydrolysis of .Coconut oil orzmay take certain .fractions of such fatty acids. The `fatty acids include laurie, .hyristic, palmitlc and .-stearic. Preferably saturated higher .fattyacids having at least 12 .carbonatoms are -used and lsometimes it may be advisable to avoid .the presence .of `any substantial amount of the unsaturated fatty acids; in :such case, the fatty acids have an. iodinenumber vofvnot .over 2.0. e .'Ifhe .relative proportions of the constituents vare such-that there is present for each mol. of .the hydroxyethylsulphuric acid salt an amount of .the fatty acid which is less than l mol.,.say 0.9.5 mol., and more than 0.6 mol. The mixture 'is heated in a closed reactionkettle. While maintaining an inert atmosphere .by the use'of a suitable gas `such asnitrQgen or .carbon dioxide. The heating :is conducted lat atemperature vof Vabout .200 to .300 C. for asufiicient length of time to complete the reaction .between the constituents. :Usually from 1 tofi 'hours 'is suflicient.. A pressure is maintained' VWhich iis' usually .somewhat .'beloW "atmosf phericgbut in all casesabove'250fmm. After `the Application Maren .-9, 195og serial No. 148,692

substantial completion ofthe reaction 4the prese sure is reduced to below mm. and'preferably to as low a point as practical in ordinary produc.- tion equipment, say, from'lO :to 20 mm.. The heating is continued for a suicient `length of time at the high vacuum to volatilize andremove any'unreacted fatty acid present in the reaction product. vit is desirable that'the product have a very low free fatty acid number, say,not-over V5.0 and often as 10W as 2.0.

Usually a considerable .excess of the hydroxy.- ethylsulphuric acid salt is used and lt may be desirable to remove such excess from thereactlon product. This can be accomplished by dissolving the reaction product in water and recrystallizing the same by usual methods, whereby the hydroxyethylsulphuric acid saltrema'ins in solution. By this procedure it is found that the nalzproduct is dry and granular, and is non-fhydroscopic.

In the accompanying drawing constituting a part hereof and in which like reference charac ters indicate like parts, the singleflgureis a dia.- grammatic view of an apparatus whichmay be used in practicing the present invention.

The reactor I is a closed vessel having a stirrer 2 therein mounted on a vertical shaft :3, there actor having a well 4 therein for a thermocouple or the like. A driving means 5 is provided for rotating the stirrer. The reactor is provided with an inlet 0 for carbon dioxide land an outlet 1 for vapors produced inthe reaction.

vapors pass through vertical pipe p8 into 4con-A denser 9, which may be water cooled, the conf.- densate passing out of the condenser through line Ii) and into a receiver IVI. Gases therefrom may be vented vthrough pipe I2 and liquid from the receiver may be drained olf through pipe I3. A receiver l 4 is provided for the purpose of catching drippings from vapor lines 'I and 8.

Connections I5 from the top and bottom of receiver II lead into receiver I6 and outlet .I 1 'therefrom is connected to ya source .of vacuum. Liquid from receiver I6 may be `removed through pipe IB. Afbypass I9 is provided from receiver I I tothe source of vacuum.

The following are examples of the operationof the invention.

Example 1.

l mol. of hydroxyethylsulphuric acid `.Sodium salt and 0.8 mol. of .a mixture Vof fatt-y acids .in which lauric acid is v,the major constituent, .containing not over of l.the adjacent `fatt-y .acids and derived from v.the fractionaldistillain of he fatty acids .of .coconutQiL .are heatedLin an :a phere of lcarbon dioxide to 220 C.-,20911 l H maintained at said temperature for 2 hours or more. The pressure is maintained at about 300 mm. absolute pressure or somewhat higher for the aforesaid period until the reaction is substantially complete.A yThe pressure is then ldecreased as rapidly as possible to not over 20 mm. and maintained at said temperature so that the total elapsed time is at least 4 hours, of which about 1.5 hours is at the lowest pressure.

The mass is cooled as rapidly as possible with continuous agitation. As the cooling proceeds the physical condition of' the reaction mass changes from a non-viscous liquid to a viscous mass and then to a brittle mass which granulates readily and forms powder or beads. After the contents of the reaction vessel have reached a relatively low temperature, say below 120 C., the mass may be removed. To further pulverize the mass to a uniform size, it is cooled to room temperature. The free fatty acid number of the product is approximately 5.0. During the entire operationoxygen is excluded from the reaction vessel.

To purify the product by removing unreacted salts, the product is dissolved in water to form a saturated solution at least 90 to 95 C. Water is evaporated to give a super-saturated solution and it is then cooled to room temperature. The product precipitates out and is separated from the mother liquor. If desired, the product may be washed with a limited amount of water. The crystallized product is substantially free from excess of hydroxyethylsulphuric acid compound.

Example 2 A mixture is made of 1 mol. equal to 148 lbs. of sodium hydroxy ethylsulphate and .8 mol., equal to 175 lbs. of commercial lauric acid. Said acid is derived by the hydrolysis of hydrogenated coconut oil and fractional distillation thereof to give a lauric acid fraction, which contains a major portion of lauric acid and a minor portion of adjacent acids. A typical mixture has a free fatty acid number of 126 to 132, a maximum iodine value of 2.0, a titre of about 24 C. as a minimum, and a saponication value of 250 to 263.

The mixture is heated in the reactor to a temperature of 220 to 260l C. in an atmosphere of CO2 and at approximately 400 mm. absolute pressure. The heating at this temperature is continued for 2 hours or more, after which the pressure is decreased rapidly to less than 20 mm. absolute pressure, while maintaining approximately the same range of temperatures. Temperature and W pressure are maintained for at least an hour and a half and suiciently long so that the total time of heating is at least 4 hours.

Heating is then discontinued and the reaction mass is cooled rapidly while maintaining the agitation and the vacuum. When no more fatty acids distill over, the vacuum may be released. The reactor should not be open to the atmosphere until the temperature has dropped below about 120 C.

Example 3 A mixture is made of 1 mol. of sodium hydroxy ethylsulphate equal to 111 lbs., with .8 mol. of commercial stearic acid, equal to 162 lbs. A typical stearic acid composition has a free fatty acid number of 99 to 105, a maximum iodine value of 3.0, a saponication value of 197 to 205, and a titre of 61 to 64 C. The procedure of Example 2 is followed.

Example 4 Example 5 Any of the above compositions may be made into a cream shampoo. In making such a shampoo a stabilizing material is used and it is dispersed in water. Then a relatively large amount of the aforesaid product, which is the detergent, is added, together with salt and lanolin. The mixture is agitated with a suitable type of agitator and is simultaneously heated preferably on a steam bath to 50'l5 C. Agitation is continued until the composition is smooth and creamy. The composition while still at elevated temperature is homogenized in a suitable mixer for about 10 minutes, poured into containers and allowed to cool. The following is a typical composition in parts by weight:

Polyvinyl alcohol 2 Water 71 Product of Example 2 23 Product of Example 3 21 Stearic acid (comm.) 1 Sodium chloride 1 Lanolin 1 Example 6 The following composition is quite suitable as a shampoo, the parts being by weight:

Lanolin 1.0

Example 7 In order to produce the detergent in a bar or cake form any one of the reaction products of Examples 1 to 4 is heated to a point substantially above room temperature, say 50 to 100 C. 5 to 10 parts by weight of water at about the boiling point is mixed thoroughly therewith. When the composition is uniform it is cast in molds to form cakes of suitable size and shape. In a typical composition 9 parts of the condensation product may be mixed with 1 part of water to form a satisfactory cake. If desired, addition agents, fillers, abrasives, coloring materials, perfumes or the like may be introduced during the mixing operation.

The procedure is based upon the discovery that the condensation products have steep solubility curves so that lwhen heavy suspensions thereof in cold water are warmed, they go through a pasty stage before giving clear solutions. In view of this an insufficient amount of water to give a clear solution when hot is introduced into the condensation product and upon cooling it rapidly goes through the pasty and then into the solid state to form a dry coherent body even though a substantial amount of water is present therein.

Although the invention has been described setting forth several specic embodiments thereof, the invention is not to be limited thereto as various changes in the details of operation and of composition may be made without departing from the principles herein set forth. For instance, instead of using the sodium salt of the hydroxyethylsulphuric acid, other soluble salts may be used, as for example, the potassium salt. Such substitution may -be made in any of Examples 1 to 4. The acids used in the reaction may come from other sources than coconut oil an-d such sources may -be vegetable, animal or synthetic. Other higher fatty acids than those specically named may be substituted in part or in whole for the lauric and stearic fractions set forth in the specific examples. The proportions of the constituents may be varied to some degree and the excess thereof may be removed in a suitable manner or may be allowed vto remain in the final product in such cases where the presence of the excess is not detrimental. The time, temperature and pressure of operation may be varied in co-relation so as to give the same results as set forth in Examples 1 and 2.

These and other changes in the details of the invention may be made within the scope thereof and the invention is, therefore, to be broadly construed and not to be limited except by the character of the claims appended hereto.

We claim:

l. A method of making detergents which comprises mixing 1 mol. of a water-soluble hydroxyethylsulphuric acid salt with an amount of a higher fatty acid less than 1 and more than 0.6 mol., maintaining an inert atmosphere, heating said mixture to a temperature of 200-300 C. for a sufficient length of time to cause a substantial reaction to occur between said substances, the pressure being below atmospheric but above 250 mm., thereafter decreasing the pressure to below 100 mm., continuing the heating to remove free fatty acid.

2. A method of making detergents which comprises mixing 1 mol. of a water-soluble hydroxyethylsulphuric acid salt with an amount of a higher fatty acid less than 1 and more than 0.6 mol., maintaining an inert atmosphere, heating said mixture to a temperature of 230-300 C. at a, pressure below atmospheric but above 250 mm. for a sufficient length of time to cause a substantial reaction to occur between said substances, thereafter decreasing the pressure to below 100 mm., continuing the heating to remove free fatty acid.

3. A method of vmaking detergents which comprises mixing 1 mol. of a Water-soluble hydroxyethylsulphuric acid salt with an amount of a fatty acid taken from the class consisting of lauric, myristic, palmitic and stearic less than 1 and more than 0.6 mol., maintaining an inert atmosphere, heating said mixture to a temperature of 230-300 C. for a sufficient length of time to cause a substantial reaction to occur between said substances, the pressure being below atmospheric but above 250 mm., thereafter decreasing the pressure to below mm., continuing the heating to remove free fatty acid.

4. A method of making detergents .which comprises mixing 1 mol. of a walter-soluble hydroxyethylsulphuric acid salt with an amount of a 'higher fatty acid less than 1 and more than 0.6 mol., maintaining an inert atmosphere, heating said mixture to a temperature of 230-300 C. for a sufficient length of time to cause a substantial reaction to occur between said substances, the pressure being below atmospheric but above 250 mm., thereafter decreasing the pressure to below 100 mm., continuing the heating to remove free fatty acid, and recrystallizing the product sc formed to remove excess of said hydroxyethylsulphuric acid salt.

5. The reaction product of 1 mol. of a Watersolu-ble hydroxyethylsulphuric acid salt with about 0.6 to 0.95 mol. of a higher fatty acid, produced by heating said reactants at 200-300 C. at pressures below atmospheric and above 250 mm. in an inert atmosphere, and thereafter continuing said heating at pressures below 100 6. The reaction product of 1 mol. of a watersoluble hydrcxyethylsulphuric acid salt with about 0.6 to 0.95 mol. of a higher saturated fatty acid, produced by heating said reactants at 200-300 C. at pressures below atmospheric and above 250 mm. in an inert atmosphere, and thereafter continuing said heating at pressures below 100 mm.

7. The reaction product of 1 mol. of a watersoluble hydroxyethylsulphuric acid salt of an alkali metal with about 0.6 to 0.95 mol. of a fatty acid, produced by heating said reactants at 200-300 C. at pressures below atmospheric and above 250 mm. in an inert atmosphere, and thereafter continuing said heating at pressures below 100 mm.

8. The reaction product of 1 mol. of a watersoluble hydroxyethylsulphuric acid salt with about 0.6 to 0.95 mol. of a higher fatty acid in the form of its alkali metal salt, produced by heating said reactants at 200-300 C. at pressures below atmospheric and above 250 mm. in an inert atmosphere, and thereafter continuing said heating at pressures below 100 mm.

HENRY A. MOLTENI. NATHANIEL H. MASARKY. GEORGE BAR/SKY.

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,175,285 Duncan Oct. 10, 1939 2,204,433 Muncie et a1 June 11, 1940 

1. A METHOD OF MAKING DETERGENTS WHICH COMPRISES MIXING 1 MOL. OF A WATER-SOLUBLE HYDROXYETHYLSULPHURIC ACID SALT WITH AN AMOUNT OF A HIGHER FATTY ACID LESS THAN 1 AND MORE THAN 0.6 MOL., MAINTAINING AN INERT ATMOSPHERE, HEATING SAID MIXTURE TO A TEMPERATURE OF 200*-300* C. FOR A SUFFICIENT LENGTH OF TIME TO CAUSE A SUBSTANTIAL REACTION TO OCCUR BETWEEN SAID SUBSTANCES, THE PRESSURE BEING BELOW ATMOSPHERIC BUT ABOVE 250 MM., THEREAFTER DECREASING THE PRESSURE TO BELOW 100 MM., CONTINUING THE HEATING TO REMOVE FREE FATTY ACID.
 5. THE REACTION PRODUCT OF 1 MOL. OF A WATERSOLUBLE HYDROXYETHYLSULPHURIC ACID SALT WITH ABOUT 0.6 TO 0.95 MOL. OF A HIGHER FATTY ACID, PRODUCED BY HEATING SAID REACTANTS AT 200*-300* C. AT PRESSURES BELOW ATMOSPHERIC AND ABOVE 250 MM., IN AN INERT ATMOSPHERE, AND THEREAFTER CONTINUING SAID HEATING AT PRESSURES BELOW 100 MM., 